CN104826361A

CN104826361A - Method for preparing a composition comprising perfluoropolyether having a carboxyl group at one terminal and method for increasing a ratio of the composition

Info

Publication number: CN104826361A
Application number: CN201510054403.9A
Authority: CN
Inventors: 山根祐治; 坂野安则
Original assignee: Shin Etsu Chemical Co Ltd
Current assignee: Shin Etsu Chemical Co Ltd
Priority date: 2014-02-06
Filing date: 2015-02-03
Publication date: 2015-08-12
Anticipated expiration: 2035-02-03
Also published as: TW201532652A; KR102311165B1; EP2905298A1; TWI632943B; JP2015164906A; JP6195414B2; US20150218311A1; EP2905298B1; KR20150093125A; US9217059B2; CN104826361B

Abstract

The present invention provides a method for preparing a composition comprising perfluoropolyether having a carboxyl group at one terminal and a method for increasing a ratio of the composition. The method for increasing a ratio of the composition includes steps as follows: subjecting the composition comprising perfluoropolyether having a carboxyl group at one terminal and the composition comprising perfluoropolyether having carboxyl groups at two terminals to chromatography in which a moving phase is supercritical or subcritical state carbon dioxide of the specific temperature and the specific pressure, wherein, the specific temperature is in the range of 25 DEG C to 150 DEG C, and the specific pressure is in the range of 7MPa to 30MPa,and a stationary phase is silica gel to thereby collect a fraction containing the perfluoropolyether having a carboxyl group at one terminal at a higher ratio. The method can efficiently provide the composition comprising perfluoropolyether having a carboxyl group at one terminal at a higher ratio.

Description

The manufacture method of the composition containing the carboxylic per-fluoro polyether compound of single end and improve the method for containing ratio of described compound

Technical field

The present invention relates to a kind of method of manufacture method containing the composition of the carboxylic per-fluoro polyether compound of single end with high concentration and the containing ratio improving described compound.

Background technology

At single end, there is the per-fluoro polyether compound (hereinafter referred to as single terminal derivative thing) of functionality base or be often used as the predecessor of the various derivative such as surfactant or surface conditioning agent at the per-fluoro polyether compound (hereinafter referred to as two terminal derivative things) (being referred to as functional initiator below) that two ends have a functionality base.Such as, the predecessor for the useful surfactant of the polymerization of polymer can be enumerated: the acrylic acid derivative of described functional initiator, amine derivative, isocyanate derivates.In addition, the predecessor of surface conditioning agent can enumerate the alkoxyl derivatives, chlorine derivative, silazane derivatives etc. of described functional initiator.

Single terminal derivative thing has different character from two terminal derivative things.Such as, two terminal derivative things can cause chain length to extend or gelation, but single terminal derivative thing can not cause this reaction.In addition, if in the composition containing all not there is the what is called of functional group without functional initiator at arbitrary end, then sometimes can produce the problem as under-ageing when hardening.Therefore, the containing ratio improving functional initiator composition is industrially important.In addition, in this description, so-called " functionality " refers to have reactive functional group, and so-called " without functionality " refers to not have reactive functional group.

In addition, there is-(OCF ₂) _p(OCF ₂cF2) _q(OCF ₂cF ₂cF ₂) _r(OCF ₂cF ₂cF ₂cF ₂) _s-the polymer that has a functionality base as single end of the per-fluoro polyether compound of backbone structure is difficult to manufacture (in described formula, p, q are the integer of 5 ~ 300 independently of one another, r, s are the integer of 0 ~ 80 independently of one another, and p+q+r+s=10 ~ 500).Record in patent document 1: the predecessor of both-terminal-functional per-fluoro polyether compound local is fluoridized, after obtaining one-terminal-functional per-fluoro polyether compound, both-terminal-functional per-fluoro polyether compound and the mixture without functionality per-fluoro polyether compound thus, carry out separation and purification by distillation, manufacture the composition of the one-terminal-functional per-fluoro polyether compound containing specified quantitative thus.But the method recorded in patent document 1 utilizes the boiling-point difference of each composition to be separated, if therefore the molecular weight distribution of each composition is not narrow, then cannot apply.The upper limit of molecular weight is below distillable size, and the upper limit in embodiment terminates in mean molecule quantity 1, about 000.Therefore, be difficult to be applied to high molecular weight components.

If can manufacture when not restriction molecule amount or molecular weight distribution the composition containing one-terminal-functional per-fluoro polyether compound with high concentration, be then suitable for use as surface conditioning agent, lubricant and elastomeric material.Therefore, expect to develop a kind of can be applied to broad molecular weight scope polymer and the method for the composition containing one-terminal-functional per-fluoro polyether compound with high concentration can be manufactured.

Record in patent document 2 and patent document 3: first both-terminal-functional polymer local is fluoridized, manufacture one-terminal-functional polymer, both-terminal-functional polymer and without after the mixture (content of one-terminal-functional polymer is high) of functional initiator, by raw the removing without functional initiator of by-product.Record in patent document 2 and patent document 3: when both-terminal-functional polymer local is fluoridized, limited by the amount of adjustment fluorine gas and fluoridize and reduce the remaining of both-terminal-functional polymer, a large amount of composition containing one-terminal-functional polymer can be obtained.But, when the method, also generate without functional initiator in a large number simultaneously.In patent document 2 and patent document 3, as the removing method without functional initiator, describe the absorption method or Thin film evaporation techniques that utilize ion exchange resin.

Patent document 4 relates to a kind of manufacture method of magnetic recording media fluorine base lubricant, and record: the fluorine base lubricant having imported the functional groups such as piperonyl (piperonyl) at two ends to be carried out using supercritical carbon dioxide as mobile phase and using silica gel (silica gel) as the chromatography (Chromatography) of Stationary liquid, be separated into multiple component (fraction), from the component of gained, select the component that functional group's Drug delivery rate is high, manufacture thus average functional group's Drug delivery rate high, especially more than 95% fluorine base lubricant.Record in patent document 4: by described method, make the terminal-modified rate of both-terminal-functional polymer bring up to 99% by about 90%.

[prior art document]

[patent document]

[patent document 1] Japan Patent spy table 2009-532432 publication

[patent document 2] Japanese Patent Laid-Open 2012-233157 publication

[patent document 3] Japanese Patent Laid-Open 2012-72272 publication

[patent document 4] Japanese Patent Laid-Open 2001-164279 publication

Summary of the invention

[invention institute for solution problem]

But that records in patent document 2 and patent document 3 utilizes in the adsorption method of ion exchange resin, needs the such as ion exchange resin of about 2 times amount and the fluorous solvent of 9 times amount, and then need hydrochloric acid relative to polymer.Therefore be unsuitable for volume production, manufacture efficiency poor.In addition, fluorine series solvent is not only expensive, and causes dysgenic danger large to operator or environment.And then, sometimes removing stripping from ion exchange resin ion component or organic in take great energy.On the other hand, utilize the separation of thin-film distillation to be use boiling-point difference to be separated, therefore separating power is poor.In addition, molecular weight is larger, because more diminishing with or without the boiling-point difference caused by functional group, to be therefore more difficultly separated.Therefore, the problems such as the poor performance of product are had.

In addition, the method recorded in patent document 4 is in order to by without the removing of functionality per-fluoro polyether compound, acquisition to contain the effective ways of the composition of both-terminal-functional polymer with high concentration, but cannot be selective and obtain the composition containing one-terminal-functional polymer with high concentration efficiently.

Therefore, the object of the present invention is to provide a kind of efficient and manufacture the method for the composition containing the carboxylic per-fluoro polyether compound of single end with high concentration with high selection rate.

[solving the technological means of problem]

The critical-temperature of carbon dioxide is 31.1 DEG C, and critical pressure is 7MPa, becomes supercriticality, therefore processing ease compared with other materials under relatively mild condition.Supercritical fluid apparent temperature and pressure and variable density, can control solute dissolves ability, can dissolve per-fluoro polyether compound.The dissolubility of per-fluoro polyether compound in supercritical carbon dioxide look functional group kind or with or without and different.In addition, dissolubility also looks molecular weight and different, has the tendency of dissolving under the condition of milder when molecular weight is little.Therefore, by means of only supercritical extract according to the kind of functional group or have no-trump have molecular weight distribution polymer be separated very difficulty, molecular weight distribution sharp must be made in advance.

But, the present inventor etc. have carried out making great efforts research, found that, by utilizing carboxyl in advance, modification is carried out to the terminal functional group of terminal-functional per-fluoro polyether compound, and using the carbon dioxide of the supercriticality or subcritical state with specific temperature and pressure condition as mobile phase, pass through in the chromatograph of Stationary liquid using silica gel, per-fluoro polyether compound can be separated efficiently according to the presence or absence of carboxyl, the component containing the carboxylic per-fluoro polyether compound of single end with high concentration can be obtained easily.

Namely, the invention provides following methods (hereinafter referred to as the first method), described method improves the containing ratio of the carboxylic per-fluoro polyether compound of single end through following operation: for the composition containing the carboxylic per-fluoro polyether compound of single end and the carboxylic per-fluoro polyether compound of two ends, carry out using the carbon dioxide of supercriticality or subcritical state as mobile phase and using silica gel as the chromatography of Stationary liquid, now, mobile phase is set as be in more than 25 DEG C and temperature (T) between less than 150 DEG C and be in more than 7MPa and the state of pressure (P) between below 30MPa, carry out chromatography, divide and get the component containing the carboxylic per-fluoro polyether compound of single end with high concentration.

In addition, the invention provides following methods (hereinafter referred to as the second method): for containing the carboxylic per-fluoro polyether compound of single end, the carboxylic per-fluoro polyether compound of two ends and all not there is at arbitrary end the composition of per-fluoro polyether compound (hereinafter referred to as without functionality compounds) of carboxyl, carry out using the carbon dioxide of supercriticality or subcritical state as mobile phase and using silica gel as the chromatography of Stationary liquid, now, through arbitrary operation of following (i ') or (ii '), improve the containing ratio of the carboxylic per-fluoro polyether compound of single end.

Mobile phase is set as being in more than 25 DEG C and temperature (T between less than 150 DEG C by (i ') _o) and be in more than 7MPa and be less than the pressure (P between 30MPa ₁) state, carry out chromatography, point to get with high concentration containing the component with or without functionality compounds, then, by the pressure setting of mobile phase for be in more than 7MPa and between below 30MPa and higher than described pressure (P ₁) pressure (P ₂) state, carry out chromatography, point to get the operation of the component containing the carboxylic per-fluoro polyether compound of single end with high concentration

Mobile phase is set as being in more than 25 DEG C and temperature (T between less than 150 DEG C by (ii ') ₁) and be in more than 7MPa and pressure (P between below 30MPa _o) state, carry out chromatography, point to get with high concentration containing the component with or without functionality compounds, then, the temperature of mobile phase is set as being in more than 25 DEG C and is less than between 150 DEG C and lower than described temperature (T ₁) temperature (T ₂) state, carry out chromatography, point to get the operation of the component containing the carboxylic per-fluoro polyether compound of single end with high concentration.

In addition, the invention provides a kind of method that content manufacturing the carboxylic per-fluoro polyether compound of single end is the composition of more than 80 % by mole, it is the composition of more than 80 % by mole by the content that described method manufactures the carboxylic per-fluoro polyether compound of single end.

[effect of invention]

Method of the present invention can provide the composition containing the carboxylic per-fluoro polyether compound of single end with high concentration efficiently.In addition, method of the present invention is little due to molecule quantitative limitation, therefore can be applied to the per-fluoro polyether compound with broad molecular weight.And then method of the present invention can reduce the use amount of fluorine series solvent, therefore little on the impact of carrying capacity of environment, be also suitable for volume production.

Detailed description of the invention

Below, the present invention is described in detail.

First method of the present invention is the method for the composition containing the carboxylic per-fluoro polyether compound of single end and the carboxylic per-fluoro polyether compound of two ends being carried out to purifying.Described method is through following operation: carry out using the carbon dioxide of supercriticality or subcritical state as mobile phase to described composition, and the chromatography (hereinafter referred to as Supercritical fluid chromatography analysis) using silica gel as Stationary liquid, now, mobile phase is set as be in more than 25 DEG C and less than 150 DEG C, preferably greater than 25 DEG C and the temperature (T) be less than between 150 DEG C and be in more than 7MPa and below 30MPa, the state of the pressure (P) between 30MPa is less than preferably greater than 7MPa, carry out chromatography, divide and get the component containing the carboxylic per-fluoro polyether compound of single end with high concentration.

Described first method of the present invention also may further include the operation of following (i) or (ii).

I () is after point getting the operation of described component, by the pressure setting of mobile phase for being in more than 7MPa and the state of pressure (P ') between below 35MPa and higher than described pressure (P), carry out chromatography, divide the operation of getting a large amount of components containing the carboxylic per-fluoro polyether compound of two ends.In this operation, the temperature of mobile phase keeps described temperature (T).Wherein, temperature also can change slightly.

(ii) after point getting the operation of described component, the temperature of mobile phase is set as being in more than 25 DEG C and is less than between 100 DEG C and the state of temperature (T ') lower than described temperature (T), carry out chromatography, divide the operation of getting a large amount of components containing the carboxylic per-fluoro polyether compound of two ends.In this operation, the pressure of mobile phase keeps described pressure (P).Wherein, pressure also can change slightly.

Can be divided by these operations and get a large amount of component containing the carboxylic per-fluoro polyether compound of two ends.

By through described operation, the composition (component) containing one-terminal-functional per-fluoro polyether compound with high concentration can be obtained.That is, the containing ratio of the one-terminal-functional per-fluoro polyether compound in composition can be improved.The so-called described composition (component) containing one-terminal-functional per-fluoro polyether compound with high concentration, refers to preferably more than 80 % by mole, more preferably more than 90 % by mole and then preferably more than 95 % by mole and contain the composition (component) of one-terminal-functional per-fluoro polyether compound.Such as relative to the total mole of one-terminal-functional per-fluoro polyether compound and both-terminal-functional per-fluoro polyether compound, with preferably more than 80 % by mole, more preferably more than 90 % by mole and then preferably more than 95 % by mole and containing one-terminal-functional per-fluoro polyether compound.In addition, in the present invention, the pressure of so-called mobile phase refers to the pressure of the mobile phase in high-pressure bottle, and the temperature of so-called mobile phase refers to the temperature of the mobile phase in high-pressure bottle.

Carbon dioxide as mobile phase has supercriticality or subcritical state.The critical-temperature of carbon dioxide is 31.1 DEG C, and critical pressure is 7MPa.In the present invention, carbon dioxide can be also supercriticality, also can be subcritical state.The pressure limit of the carbon dioxide used in method of the present invention is for more than 7MPa and below 35MPa, preferred more than 8MPa and below 30MPa.In addition, the temperature range of this carbon dioxide is more than 25 DEG C and less than 150 DEG C, preferably more than 30 DEG C and the scope of less than 100 DEG C.There is no particular restriction for the flow of mobile phase, as long as suitably select.When extraction container is large, preferably augmented flow.As long as the capacity of extraction container is suitably selected according to the amount of the composition carrying out purifying.

In the method comprising described operation (i), preferably the temperature of mobile phase is certain.When the temperature of mobile phase is certain, the pressure of mobile phase is higher, and the dissolubility of compound in mobile phase with functional group more uprises.The pressure P of mobile phase, pressure P ' be set according to the molecular weight of polymer contained in composition and extraction temperature T.Such as contained in the composition polymer has 1, more than 000 and 15, less than 000 weight average molecular weight when, extraction temperature T to be in more than 25 DEG C and temperature in the scope of less than 150 DEG C is advisable, more preferably to be in more than 30 DEG C and temperature in the scope of less than 80 DEG C is advisable.Now, pressure P is be in more than 7MPa and the scope of below 30MPa, be less than scope, more preferably more than the 8MPa of 30MPa and the pressure in the scope of below 25MPa preferably greater than 7MPa, pressure P ' and to be in more than 8MPa and the scope of below 35MPa, preferably more than 10MPa and below 30MPa, more preferably more than 15MPa and pressure in the scope of below 30MPa are advisable.Wherein, pressure P ' higher than described pressure P.Now, also can make pressure pressure P and pressure P ' between periodically change.

In the method comprising described operation (ii), preferably the pressure of mobile phase is certain.When the pressure of mobile phase is certain, the temperature of mobile phase is lower, and the dissolubility of compound in mobile phase with functional group more uprises.The temperature T of mobile phase, temperature T ' set according to the molecular weight of polymer contained in composition and extracting pressure P.Such as contained in the composition polymer has 1, more than 000 and 15, less than 000 weight average molecular weight when, extracting pressure P to be in more than 7MPa and pressure in the scope of below 30MPa is advisable, more preferably to be in more than 8MPa and pressure in the scope of below 25MPa is advisable.Now, temperature T is in more than 28 DEG C and is less than scope, preferably more than 30 DEG C and the scope of less than 100 DEG C, more preferably more than 30 DEG C of 150 DEG C and the temperature in the scope of less than 80 DEG C, and temperature T ' is to be in more than 25 DEG C and to be less than scope, preferably more than 25 DEG C and the scope of less than 80 DEG C, more preferably more than 25 DEG C of 100 DEG C and the temperature in the scope of less than 60 DEG C is advisable.Wherein, temperature T ' is lower than described temperature T.Now, extraction temperature also can be made periodically to change between extraction temperature T and extraction temperature T '.

Second method of the present invention is the method for the composition being included in arbitrary end further and all not having the per-fluoro polyether compound (hereinafter referred to as without functionality per-fluoro polyether compound) of carboxyl being carried out to purifying.That is, the composition carrying out chromatography contains one-terminal-functional per-fluoro polyether compound, both-terminal-functional per-fluoro polyether compound and without functionality per-fluoro polyether compound.The method is through arbitrary operation of following (i ') or (ii ').

Mobile phase is set as being in more than 25 DEG C and temperature (T between less than 150 DEG C by (i ') _o) and be in more than 7MPa and be less than the pressure (P between 30MPa ₁) state, carry out chromatography, point to get with high concentration containing the component with or without functionality compounds, then, by the pressure setting of mobile phase for be in more than 7MPa and between below 30MPa and higher than described pressure (P ₁) pressure (P ₂) state, carry out chromatography, point to get the operation of the component containing the carboxylic per-fluoro polyether compound of single end with high concentration.In this operation, the temperature of mobile phase keeps described temperature (T _o).Wherein, temperature also can change slightly.

Mobile phase is set as being in more than 25 DEG C and temperature (T between less than 150 DEG C by (ii ') ₁) and be in more than 7MPa and pressure (P between below 30MPa _o) state, carry out chromatography, point to get with high concentration containing the component with or without functionality compounds, then, the temperature of mobile phase is set as being in more than 25 DEG C and is less than between 150 DEG C and lower than described temperature (T ₁) temperature (T ₂) state, carry out chromatography, point to get the operation of the component containing the carboxylic per-fluoro polyether compound of single end with high concentration.In this operation, the pressure of mobile phase keeps described pressure (P _o).Wherein, pressure also can change slightly.

In the method comprising described operation (i '), preferably the temperature of mobile phase is certain.In addition, in the method comprising described operation (ii '), preferably the pressure of mobile phase is certain.As described in the first method explanation in described in, Supercritical fluid chromatography analyze in, when the temperature of mobile phase is certain, the pressure of mobile phase is higher, and the dissolubility of compound in mobile phase with functional group more uprises.In addition, when the pressure of mobile phase is certain, the temperature of mobile phase is lower, and the dissolubility of compound in mobile phase with functional group more uprises.Second method of the present invention is by the arbitrary operation through described (i ') or (ii '), the composition (component) containing one-terminal-functional per-fluoro polyether compound with high concentration can be obtained, the containing ratio of the one-terminal-functional per-fluoro polyether compound in composition can be improved.

The so-called composition (component) containing one-terminal-functional per-fluoro polyether compound with high concentration, refers to preferably more than 80 % by mole, more preferably more than 90 % by mole and then preferably more than 95 % by mole and contain the composition (component) of one-terminal-functional per-fluoro polyether compound.Such as relative to one-terminal-functional per-fluoro polyether compound, both-terminal-functional per-fluoro polyether compound and the total mole without functionality compounds, with preferably more than 80 % by mole, more preferably more than 90 % by mole and then preferably more than 95 % by mole and containing the composition (component) of one-terminal-functional per-fluoro polyether compound.In addition, so-called described with high concentration containing the component with or without functionality compounds, refer to preferably more than 90 % by mole, more preferably more than 95 % by mole and then preferably 100 % by mole and the component that contains with or without functionality compounds.In addition, in the present invention, the pressure of so-called mobile phase refers to the pressure of the mobile phase in high-pressure bottle, and the temperature of so-called mobile phase refers to the temperature of the mobile phase in high-pressure bottle.

Particularly in described operation (i '), P ₁for being in preferred more than 7MPa and below 25MPa, more preferably more than 7MPa and pressure between below 22MPa, P ₂to be in more than 7MPa and to be less than 30MPa, preferably more than 8MPa and to be less than 30MPa, more preferably more than 8MPa and pressure (wherein, P between below 25MPa ₂higher than P ₁) be advisable.In addition, in described operation (ii '), T ₁for being in the temperature preferably between more than 40 DEG C and less than 150 DEG C, T ₂to be in more than 28 DEG C and to be less than 150 DEG C, temperature (wherein, T preferably more than more than 30 DEG C and less than 100 DEG C, more preferably 30 DEG C and between less than 80 DEG C ₂lower than T ₁) be advisable.

Described second method of the present invention also may further include the operation of following (1 ") or (ii ").

(i ") after described (i ') operation, by the pressure setting of mobile phase for be in more than 7MPa and between below 35MPa and higher than described pressure (P ₂) pressure (P ₃) state, carry out chromatography, point to get the operation of a large amount of components containing the carboxylic per-fluoro polyether compound of two ends.In this operation, the temperature of mobile phase keeps described temperature (T _o).Wherein, temperature also can change slightly.

(ii ") after described (ii ') operation, the temperature of mobile phase is set as being in more than 25 DEG C and is less than between 100 DEG C and lower than described temperature (T ₂) temperature (T ₃) state, carry out chromatography, point to get the operation of a large amount of components containing the carboxylic per-fluoro polyether compound of two ends.In this operation, the pressure of mobile phase keeps described pressure (P _o).Wherein, pressure also can change slightly.

Can be divided by described operation and get a large amount of component containing the carboxylic per-fluoro polyether compound of two ends.

In the method through described operation (i '), the pressure P of mobile phase ₁, pressure P ₂, pressure P ₃the molecular weight according to polymer contained in composition and extraction temperature T _oset.Such as contained in the composition polymer has 1, when the weight average molecular weight of more than 000 and be less than 3,000, and extraction temperature T _ofor being in more than 25 DEG C and temperature in the scope of less than 150 DEG C, more preferably to be in more than 30 DEG C and temperature in the scope of less than 80 DEG C is advisable.Now, pressure P ₁to be in more than 7MPa and the scope of below 20MPa, preferably more than 7MPa and pressure in the scope of below 15MPa are advisable, pressure P ₂to be in more than 8MPa and the scope of below 25MPa, preferably more than 10MPa and pressure in the scope of below 20MPa are advisable.Wherein, pressure P ₂higher than described pressure P ₁.In addition, when comprising described operation, (i "), pressure P 3 is to be in more than 10MPa and the scope of below 30MPa, preferably more than 15MPa and pressure in the scope of below 30MPa are advisable.Wherein, pressure P ₃higher than described pressure P ₂.

Polymer contained in the composition has 3, more than 000 and be less than 5000, particularly more than 3000 and the weight average molecular weight of 4, less than 500 when, extraction temperature T _ofor being in more than 25 DEG C and temperature in the scope of less than 150 DEG C, more preferably to be in more than 30 DEG C and temperature in the scope of less than 80 DEG C is advisable.Now, pressure P ₁to be in more than 7MPa and the scope of below 20MPa, preferably more than 8MPa and pressure in the scope of below 18MPa are advisable, pressure P ₂to be in more than 8MPa and the scope of below 27MPa, preferably more than 10MPa and pressure in the scope of below 22MPa are advisable.Wherein, pressure P ₂higher than described pressure P ₁.In addition, when comprise described operation (i "), pressure P ₃to be in more than 10MPa and the scope of below 30MPa, preferably more than 15MPa and pressure in the scope of below 30MPa are advisable.Wherein, pressure P ₃higher than described pressure P ₂.

In addition, polymer contained in the composition has 5, more than 000 and the weight average molecular weight of 7, less than 000 when, extraction temperature T _ofor being in more than 25 DEG C and temperature in the scope of less than 150 DEG C, more preferably to be in more than 30 DEG C and temperature in the scope of less than 80 DEG C is advisable.Now, pressure P ₁for being in more than 7MPa and the scope of below 22MPa, preferably more than 8MPa and pressure in the scope of below 20MPa, pressure P ₂to be in more than 8MPa and to be less than scope, preferably more than the 10MPa of 30MPa and the pressure in the scope of below 25MPa is advisable.Wherein, pressure P ₂higher than described pressure P ₁.In addition, when comprise described operation (i "), pressure P ₃to be in more than 10MPa and the scope of below 30MPa, preferably more than 15MPa and pressure in the scope of below 30MPa are advisable.Wherein, pressure P ₃higher than described pressure P ₂.

In the method through described operation (ii '), the temperature T of mobile phase ₁, temperature T ₂and temperature T ₃the molecular weight according to polymer contained in composition and extracting pressure P _oset.Such as contained in the composition polymer has 3, more than 000 and the weight average molecular weight of 5, less than 000 when, extracting pressure P _opreferably be in more than 7MPa and pressure in the scope of below 30MPa, more preferably to be in more than 8MPa and pressure in the scope of below 25MPa is advisable.Now, temperature T ₁for being in more than 40 DEG C and the scope of less than 150 DEG C, preferably more than 50 DEG C and temperature in the scope of less than 100 DEG C, temperature T ₂to be in more than 30 DEG C and the scope of less than 100 DEG C, preferably more than 35 DEG C and the scope of less than 90 DEG C, particularly preferably more than 40 DEG C and temperature in the scope of less than 80 DEG C are advisable.Wherein, temperature T ₂lower than described temperature T ₁.In addition, when comprise described operation (ii "), temperature T ₃to be in more than 25 DEG C and the scope, preferably more than 25 DEG C and the temperature in the scope of less than 60 DEG C that are less than 100 DEG C are advisable.Wherein, temperature T ₃lower than described temperature T ₂.

In described first method and the second method, as long as divide the time of getting each component suitably to set according to the molecular weight of polymer contained in composition and allotment ratio.Such as, the structure of compound contained in the component of institute's stripping can also be monitored.Monitoring such as can be undertaken by the absorption of infrared ray (Infrared, IR).

The Stationary liquid used in described first method and the second method is silica gel.Silica gel suitably can select the silica gel of existing well-known such as commercially available product.The shape of silica gel is preferably spherical.The particle diameter of silica gel preferably 30 μm ~ 300 μm, more preferably 40 μm ~ 100 μm.In addition, silica gel preferably has neutral pH value to weakly acidic scope, the scope that the pH value at 25 DEG C when more preferably colloidal silica dispersion being made in water 10 % by weight suspension is in 5 ~ 7.5 so that be preferably in 6.5 ~ 7.5 scope in be advisable.If use the silica gel of alkalescence, then carboxyl is had to be captured (trap) and irretrievable worry.The pH value of described silica gel is the value measured according to the method recorded in Japanese Industrial Standards' (Japanese Industrial Standard, JIS) Z 0701 " packaging silica-gel desiccant ".

If use in patent document 3 and record such ion exchange resin as Stationary liquid, then cannot obtain the component containing the carboxylic per-fluoro polyether compound of single end with high concentration.In contrast, method of the present invention is by being set as described silica gel by Stationary liquid, the component containing the carboxylic per-fluoro polyether compound of single end with high concentration can be obtained.

Composition containing the carboxylic per-fluoro polyether compound of single end

The composition used in method of the present invention is the composition containing the carboxylic per-fluoro polyether compound of single end and the carboxylic per-fluoro polyether compound of two ends.Or for containing the carboxylic per-fluoro polyether compound of single end, the carboxylic per-fluoro polyether compound of two ends and the composition without functionality per-fluoro polyether compound.The functional group's modification being positioned at the end of compound must be become carboxyl by the composition being carried out chromatography by manufacture method of the present invention.

So-called described per-fluoro polyether compound, refers to and has-C _jf _2jthe compound of the poly-fluorine oxyalkylene structure of multiple bonds of the repetitive represented by O-(in this structure, j be more than 1 integer, preferably 1 ~ 6 integer, more preferably 1 ~ 4 integer).Particularly be advisable with this repetitive containing 10 ~ 500, preferably 15 ~ 200, more preferably 20 ~ 100 and then preferably 25 ~ 80.

Described repetitive-C _jf _2jo-can be any one of straight chain type and branching type.Such as can enumerate following unit, also can be the unit of the two or more bonds of these repetitives.

-CF ₂O-

-CF ₂CF ₂O-

-CF ₂CF ₂CF ₂O-

-CF(CF ₃)CF ₂O-

-CF ₂CF ₂CF ₂CF ₂O-

-CF ₂CF ₂CF ₂CF ₂CF ₂O-

-C(CF ₃) ₂O-

Described poly-fluorine oxyalkylene structure is particularly by-(CF ₂) _d-(OCF ₂) _p(OCF ₂cF ₂) _q(OCF ₂cF ₂cF ₂) _r(OCF ₂cF ₂cF ₂cF ₂) _s-O (CF ₂) _d-represented (in formula, d is the integer of 0 or 1 ~ 5, and p, q are separately the integer of 5 ~ 300, and r, s are separately the integer of 0 ~ 100, and p+q+r+s=10 ~ 500, preferably 15 ~ 200, each unit shown in parantheses also can random bond).

The carboxylic per-fluoro polyether compound of single end is the compound having described poly-fluorine oxyalkylene structure and have carboxyl at single end.Such as can be represented by following formula (a).

A-Rf-B (a)

In formula (a), Rf is the poly-fluorine oxyalkylene of straight-chain or branching type, with-the OC containing 10 ~ 500, preferably 15 ~ 200, more preferably 20 ~ 100 and then preferably 25 ~ 80 _jf _2j-represented (in formula, j is described above) repetitive is advisable.

Described Rf is particularly preferably-(CF ₂) _d-(OCF ₂) _p(OCF ₂cF ₂) _q(OCF ₂cF ₂cF ₂) _r(OCF ₂cF ₂cF ₂cF ₂) _s-O (CF ₂) _d-represented poly-fluorine oxyalkylene (in formula, d, p, q, r, s are described above).

More preferably with in the molecule to be separately 5 ~ 80 and to add up to the mode becoming 20 ~ 150 to contain (OCF ₂) represented by unit and (OCF ₂cF ₂) represented by unit be advisable.

In described formula (a), A and B is carboxyl or-CF ₃base, any one of A and B is carboxyl.

The carboxylic per-fluoro polyether compound of two ends is the compound having described poly-fluorine oxyalkylene structure and have carboxyl at two ends.Such as can be represented by following formula (b).

HOOC-Rf-COOH (b)

(in described formula, Rf is described above)

It is the compound that there is described poly-fluorine oxyalkylene structure and all not there is at arbitrary end carboxyl without functionality per-fluoro polyether compound.Such as can be represented by following formula (c).

F ₃C-Rf-CF ₃(c)

(in described formula, Rf is described above)

Composition containing the carboxylic per-fluoro polyether compound of single end prepares by being fluoridized the terminal groups of both-terminal-functional per-fluoro polyether compound local.When this local is fluoridized, can control to fluoridize by adjusting the amount of fluorine gas that supply and adjust the rate of fluoridizing.The rate of fluoridizing of terminal groups is 50% ~ 90%, more preferably 60% ~ 90%, particularly preferably 65% ~ 85%.If rate of fluoridizing is lower than described lower limit, then the containing ratio of both-terminal-functional polymer becomes many, if be greater than described higher limit, then the containing ratio without functional initiator becomes many.Cause the rate of recovery step-down of one-terminal-functional polymer thus, therefore not good enough.

The content particularly carrying out in the composition before chromatography the contained carboxylic per-fluoro polyether compound of two ends is advisable with following content: relative to the total mole of the carboxylic per-fluoro polyether compound of two ends and the carboxylic per-fluoro polyether compound of single end, preferably less than 35 % by mole, more preferably less than 30 % by mole, and then preferably less than 20 % by mole, and then more preferably less than 15 % by mole.By meeting this condition, and divide the containing ratio getting the carboxylic per-fluoro polyether compound of single end to be more than 85 % by mole more reliably, the component of preferably more than 90 % by mole, more preferably more than 95 % by mole.

About the preparation of the composition containing the carboxylic per-fluoro polyether compound of single end, such as, can be prepared by the terminal carboxyl group of two ends carboxylic per-fluoro polyether compound local is fluoridized.Or also can prepare in the following manner: the terminal functional group local at two ends with the per-fluoro polyether compound of the functional group of not carboxyl is fluoridized, then remaining terminal functional group's modification is become carboxyl.The functional group of so-called not carboxyl, can enumerate hydroxyl, ester group, acid chloride group and acyl fluorides base.Preferred acyl fluorides base (-C (=O)-F).As long as described functional group is changed into the method for carboxyl according to existing well-known method.Such as can by making acyl fluorides base and water effect and being transformed into carboxyl.

Method of the present invention can efficiently and easily manufacture with high concentration, preferably more than 80%, more preferably more than 90% and then preferably more than 95% and containing the composition of the carboxylic per-fluoro polyether compound of single end.In addition, manufacture method of the present invention can the per-fluoro polyether compound of structure using there is as being only manufactured on two ends the polymer of functionality base as raw material, manufacture and contain the composition at single end with the polymer of functionality base with high concentration.In addition, in method of the present invention, about the molecular weight of polymer, as long as can be dissolved in carbon dioxide, go for the polymer of broad molecular weight.Particularly preferably be to be applied to and have 1,000 ~ 100,000 and then 1, the purifying of the per-fluoro polyether compound of the weight average molecular weight of 000 ~ 15,000.

As mentioned above, use in patent document 3 and record the isolation and purification method of such ion exchange resin owing to using a large amount of fluorine series solvents and hydrochloric acid, be therefore unsuitable for volume production.In addition, utilize the purifying of thin-film distillation cannot obtain the composition containing the carboxylic per-fluoro polyether compound of single end with high concentration, may deterioration as the performance of product when volume production.In contrast, method of the present invention does not hinder production, can manufacture efficiently and there is high performance product.Therefore, useful when manufacturing the raw material that surface conditioning agent, lubricant, elastomeric material etc. use.

Such as, import the group with water-disintegrable base by the carboxyl terminal at the composition by manufacture method gained of the present invention, can provide and contain the composition at single end with the per-fluoro polyether compound of water-disintegrable base with high concentration.Said composition can be used as surface conditioning agent suitably.In addition, be not limited thereto, well-known method can be utilized to be transformed into the various derivatives such as acrylic acid derivative, amine derivative, isocyanate derivates.

What is called has the group of water-disintegrable base, such as, can enumerate following shown group.

[changing 1]

(in formula, R is the alkyl or phenyl of carbon number 1 ~ 4, and X is water-disintegrable base, and a is 2 or 3)

In described formula (1), X is can mutually different water-disintegrable base.This X can enumerate: the alkoxyl of the carbon numbers 1 ~ 10 such as methoxyl group, ethyoxyl, propoxyl group, butoxy, the oxygen base alkoxyl of the carbon number such as methoxymethoxy, methoxy ethoxy 2 ~ 10, the acyloxy of the carbon numbers such as acetoxyl group 1 ~ 10, the alkene oxygen base of the carbon numbers such as different propenyloxy group 2 ~ 10, the halogen radicals etc. such as chloro, bromo, iodo.Wherein, it is suitable that methoxyl group, ethyoxyl, different propenyloxy group, chloro.

In described formula (1), R is the alkyl or phenyl of carbon number 1 ~ 4, wherein it is suitable that methyl.A is 2 or 3, from reactive, to the adhesion of base material viewpoint, and preferably 3.

Single end with the group represented by described formula (1) can be represented by following formula (2) containing the per-fluoro polyether compound of water-disintegrable base.

[changing 2]

(in formula, Rf base is described above, and A is-CF ₃base.Q is divalent organic group, and Z is the organopolysiloxane residue of divalent ~ 8 valency with siloxane bond, R and X is described above.A be 2 or 3, b be the integer of 1 ~ 7, c is the integer of 1 ~ 10, and α is 0 or 1)

In described formula (2), Q is divalent organic group, is the concatenating group of Rf base and Z base or Rf base and-(CH ₂) _cthe concatenating group of-Ji.Preferably can the organic group of carbon number 2 ~ 12 containing the more than one key be selected from the cohort that is made up of amido link, ehter bond, ester bond or vinyl bonds.More preferably can the divalent alkyl of the carbon number 2 ~ 12 being unsubstituted or being substituted containing the more than one key be selected from the cohort that is made up of amido link, ehter bond, ester bond or vinyl bonds.Such as following radicals can be enumerated.

[changing 3]

-CH ₂OCH ₂CH ₂-

-CF ₂OCH ₂CH ₂CH ₂-

n＝2-4

In described formula (2), Z is the organopolysiloxane residue of divalent ~ 8 valency with siloxane bond, and is chain or the ring-type organopolysiloxane residue of silicon atom number 2 ~ 13, preferably silicon atom number 2 ~ 5.Wherein, also can containing 2 silicon atoms through the silicon alkylen structures of alkylidene bond, i.e. Si-(CH ₂) _n-Si (in described formula, n is the integer of 2 ~ 6).

This organopolysiloxane residue with have carbon number 1 ~ 8, more preferably 1 ~ 4 alkyl or phenyl be advisable.In addition, the alkylidene in silicon alkylene base key is a surname with carbon number 2 ~ 6, preferably 2 ~ 4.

This Z can enumerate following shown group.

[changing 4]

As long as the importing with the group of water-disintegrable base is according to existing well-known method, such as, can use the method recorded in Japanese Patent Laid-Open 2012-72272 publication (patent document 3) and Japanese Patent Laid-Open 2012-233157 publication (patent document 2).Such as can by importing the group with water-disintegrable base through following operation (1) ~ operation (3).

(1) use the reduction of metal hydride to carrying out containing the composition at end with the per-fluoro polyether compound of carboxyl or use the contact hydrogenation of noble metal catalyst, making a part for terminal carboxyl group become hydroxyl.Metal hydride such as can use two (2-methoxy ethoxy) aluminium sodium of hydrogenation etc.Noble metal catalyst such as can use ruthenium.

(2) then, aliphatic unsaturated group is imported to terminal hydroxyl.As long as introduction method is according to existing well-known method.Aliphatic unsaturated group such as can enumerate the thiazolinyl of carbon number 2 ~ 12.Such as make by the polymer composition of described operation (1) gained, react under the existence of hydrogen sulfate TBuA with the alkenyl halide compound such as allyl bromide, bromoallylene after, drip NaOH and be adjusted to alkalescence, importing the thiazolinyls such as pi-allyl at the end of polymer thus.

(3) then, hydrolysable silanes base is imported to terminal aliphatic race unsaturated group.Carry out in the following manner as long as import: make by the polymer composition of described operation (2) gained, and at an end, there is SiH base and the organo-silicon compound at another end with water-disintegrable base (X) carry out addition reaction.These organo-silicon compound can enumerate the hydridosilanes etc. of end containing water-disintegrable base (X).As long as addition reaction is carried out under well-known reaction condition, as long as and carry out under the existence of addition reaction catalyst, such as platinum group compound.

By described method, can provide and contain the composition at single end with the per-fluoro polyether compound of water-disintegrable base represented by described formula (2) with high concentration.Said composition can be used as surface conditioning agent suitably.

Surface conditioning agent also can contain the local hydrolytic condensate of the per-fluoro polyether compound represented by described formula (2).This local hydrolytic condensate so-called, refer to utilize well-known method to make in advance a part for the terminal hydrolysis base of the per-fluoro polyether compound represented by described formula (2) is hydrolyzed, the product of condensation gained.

In surface conditioning agent, optionally also can add hydrolytic condensation catalyst, such as organo-tin compound (diformazan dibutyltin oxide, dibutyl tin laurate etc.), organic titanic compound (tetra-n-butyl titanate etc.), organic acid (acetic acid, methanesulfonic acid, fluorine richness carboxylic acid etc.), inorganic acid (hydrochloric acid, sulfuric acid etc.).In these compounds, particularly desirably acetic acid, tetra-n-butyl titanate, dibutyl tin laurate, fluorine richness carboxylic acid etc.As long as addition is catalytic amount.Relative to per-fluoro polyether compound and/or its local hydrolytic condensate 100 mass parts, be generally 0.01 mass parts ~ 5 mass parts, particularly 0.05 mass parts ~ 1 mass parts.

Described surface conditioning agent also can contain solvent.Solvent is preferably advisable with following solvent: fluorine richness aliphatic hydrocarbon series solvent (PF 5070, PFO etc.), fluorine richness aromatic hydrocarbon series solvent (hexafluoro meta-xylene, benzotrifluoride (benzotrifiuoride), 1, 3-trifluoromethylbenzene etc.), fluorine richness ether series solvent (methyl perfluorobutyl ether, ethyl perfluorobutyl ether, perfluor (2-butyl tetrahydrofuran) etc.), fluorine richness alkylamine series solvent (perfluorotributylamine, perfluor three amylamine etc.), hydrocarbon system solvent (benzin (petroleumbenzine), mineral spirits (mineral spirits), toluene, dimethylbenzene etc.), ketone series solvent (acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK) etc.).Wherein, from the viewpoint of dissolubility, wetting quality etc., it is desirable to the solvent (being called fluorine series solvent) through fluorine richness, particularly preferably 1,3-trifluoromethylbenzene, hexafluoro meta-xylene, perfluor (2-butyl tetrahydrofuran), perfluorotributylamine and ethyl perfluorobutyl ether.

Described solvent also can, by its two or more mixing, preferably make PFPE and/or its local hydrolytic condensate dissolve equably.In addition, as long as the optimum concentration of dissolving PFPE in a solvent is suitably selected according to the using method of surface conditioning agent, and unrestrictedly.Usually to become 0.01 % by weight ~ 30 % by weight, the mode of preferably 0.02 % by weight ~ 20 % by weight, more preferably 0.05 % by weight ~ 5 % by weight dissolves.

Surface conditioning agent can be granted on base material by vapor deposition treatment, form good film.The method of vapor deposition treatment is not particularly limited, such as, can use resistance heating manner or electron beam mode of heating.As long as curing condition is suitably selected according to surface treatment method.Such as when being granted by spraying (spray), ink-jet (ink-jet), hairbrush coating or dipping, it is desirable to the scope of room temperature (20 DEG C ± 15 DEG C) ~ 100 DEG C.In addition, from the viewpoint of what promote to react, sclerosis it is desirable to carry out under humidification.The thickness of sclerosis overlay film is according to carrying out the kind of the base material processed and suitably selecting, and is generally 0.1nm ~ 100nm, particularly 1nm ~ 20nm.

There is no particular restriction for the base material utilizing surface conditioning agent to carry out processing, and can be the various material such as paper, cloth, metal and oxide thereof, glass, plastics, pottery, quartz.Surface conditioning agent of the present invention can give water-and oil-repellency, low dynamic and marresistance to described substrate.Can be used as through SiO suitably especially ₂process and/or the glass of plasma treatment or the surface conditioning agent of quartz base plate.

The article utilizing surface conditioning agent to carry out processing such as can be enumerated: glass, hard coat film, high rigidity film, anti-reflective film, lens, optical lens and quartz base plate etc.Be particularly suitable for as being used at tempered glass and forming the inorganic agent of scolding water oil-repellent layers on the surface of the glass of anti-reflex treated.

[embodiment]

Below, illustrate that embodiment and comparative example are described in more detail the present invention, but the present invention is not by the restriction of following embodiment.In following embodiment and comparative example, the pressure of so-called mobile phase refers to the pressure of the mobile phase in high-pressure bottle, and the temperature of so-called mobile phase refers to the temperature of the mobile phase in high-pressure bottle.Hereinafter, the pH value of 10% water slurry state of pH value for measuring according to the method recorded in JIS Z 0701 " packaging silica-gel desiccant " of silica gel.Specifically, add distilled water 200ml in sample 20g, after heating at 80 DEG C 30 minutes, cool to room temperature, uses the supernatant of gained to measure pH value according to JIS Z8802 " pH value assay method ".

In embodiment and comparative example, use the mixture (composition F 50 ~ composition F 90) comprising following shown (1a), (1b) and (1c).This mixture uses fluorine gas fluoridized the two carboxylic per-fluoro polyether compound local of end represented by following formula (1b) and prepare.By controlling the Drug delivery rate of fluorine gas, and obtain the mixture respectively containing ratio (% by mole, identical below) had described in following table 1.About each composition recorded in table 1 containing ratio, get by making the Polymer adsorption with carboxylic acid be divided on sour adsorbent, and utilize ¹⁹f-nuclear magnetic resonance (Nuclear Magnetic Resonance, NMR) is determined.

[changing 5]

F ₃C(OC ₂F ₄) _p(OCF ₂) _q-OCF ₂COOH (1a)

HOOC-CF ₂-(OC ₂F ₄) _p(OCF ₂) _q-OCF ₂COOH (1b)

F ₃C(OC ₂F ₄) _p(OCF ₂) _q-OCF ₃(1c)

[table 1]

[embodiment 1]

Make the composition F 60 of 10g using supercritical carbon dioxide as mobile phase and be filled with silica gel 60N (Northeast chemical company manufacture, pH value be 6.5 ~ 7.5 the value of 10 % by weight water slurry states (25 DEG C), particle diameter is 40 μm ~ 100 μm, dry filling) 25mL high-pressure bottle in pass through.The flow of mobile phase is 15ml/min, and temperature is 40 DEG C, makes pressure be changed to 25MPa by 8MPa.First, 40 DEG C, dirty the stimulating the menstrual flow of condition of 8MPa be adjusted to supercritical carbon dioxide.Then, be 12MPa by the pressure setting of mobile phase.Divide under the state of the pressure 12MPa of mobile phase and get component 60 minutes, then by the pressure setting of mobile phase be 18MPa and divide to get component 60 minutes, then by the pressure setting of mobile phase be 25MPa and divide to get component 60 minutes.The ratio of composition contained in each component is shown in following table 2.This component ratio utilizes ¹⁹f-NMR determines.

[table 2]

[embodiment 2]

Make the composition F 70 of 10g using supercritical carbon dioxide as mobile phase and be filled with silica gel 60N (Northeast chemical company manufacture, pH value be 6.5 ~ 7.5 the value of 10 % by weight water slurry states (25 DEG C), particle diameter is 40 μm ~ 100 μm, dry filling) 25mL high-pressure bottle in pass through.The flow of mobile phase is 15ml/min, and temperature is 40 DEG C, makes pressure be changed to 25MPa by 8MPa.First, 40 DEG C, dirty the stimulating the menstrual flow of condition of 8MPa be adjusted to supercritical carbon dioxide.Then, be 12MPa by the pressure setting of mobile phase.Divide under the state of the pressure 12MPa of mobile phase and get component 60 minutes, then by the pressure setting of mobile phase be 18MPa and divide to get component 60 minutes, then by the pressure setting of mobile phase be 25MPa and divide to get component 60 minutes.The ratio of composition contained in each component is shown in following table 3.This component ratio utilizes ¹⁹f-NMR determines.In addition, the composition extracted under 25MPa is few due to extraction quantity, therefore cannot analyze.

[table 3]

[embodiment 3]

Make the composition F 80 of 10g using supercritical carbon dioxide as mobile phase and be filled with silica gel 60N (Northeast chemical company manufacture, pH value be 6.5 ~ 7.5 the value of 10 % by weight water slurry states (25 DEG C), particle diameter is 40 μm ~ 100 μm, dry filling) 25mL high-pressure bottle in pass through.The flow of mobile phase is 15ml/min, and temperature is 40 DEG C, makes pressure be changed to 25MPa by 8MPa.First, 40 DEG C, dirty the stimulating the menstrual flow of condition of 8MPa be adjusted to supercritical carbon dioxide.Then be 12MPa by the pressure setting of mobile phase.Divide under the state of the pressure 12MPa of mobile phase and get component 60 minutes, then by the pressure setting of mobile phase be 18MPa and divide to get component 60 minutes, then by the pressure setting of mobile phase be 25MPa and divide to get component 60 minutes.The ratio of composition contained in each component is shown in following table 4.This component ratio utilizes ¹⁹f-NMR determines.In addition, the composition extracted under 25MPa is few due to extraction quantity, therefore cannot analyze.

[table 4]

[embodiment 4]

Make the composition F 90 of 10g using supercritical carbon dioxide as mobile phase and be filled with silica gel 60N (Northeast chemical company manufacture, pH value is 6.5 ~ 7.5 the value of 10 % by weight water slurry states (25 DEG C), particle diameter are 40 μm ~ 100 μm, dry filling) 25mL high-pressure bottle in pass through.The flow of mobile phase is 15ml/min, and temperature is 40 DEG C, makes pressure be changed to 25MPa by 8MPa.First, 40 DEG C, dirty the stimulating the menstrual flow of condition of 8MPa be adjusted to supercritical carbon dioxide.Then be 12MPa by the pressure setting of mobile phase.Divide under the state of the pressure 12MPa of mobile phase and get component 60 minutes, then by the pressure setting of mobile phase be 18MPa and divide to get component 60 minutes, then by the pressure setting of mobile phase be 25MPa and divide to get component 60 minutes.The ratio of composition contained in each component is shown in following table 5.This component ratio utilizes ¹⁹f-NMR determines.In addition, the composition extracted under 25MPa is few due to extraction quantity, therefore cannot analyze.

[table 5]

[embodiment 5]

In embodiment 5, use the composition comprising the compound 45 % by mole of the compound 50 % by mole of following formula (2a), the compound 5 % by mole of formula (2b) and formula (2c).

[changing 6]

F ₃C(OC ₂F ₄) _p(OCF ₂) _q-OCF ₂COOH (2a)

HOOC-CF ₂-(OC ₂F ₄) _p(OCF ₂) _q-OCF ₂COOH (2b)

F ₃C(OC ₂F ₄) _p(OCF ₂) _q-OCF ₃(2c)

Make described composition 10g using supercritical carbon dioxide as mobile phase and be filled with silica gel 60N (Northeast chemical company manufacture, pH value be 6.5 ~ 7.5 the value of 10 % by weight water slurry states (25 DEG C), particle diameter is 40 μm ~ 100 μm, dry filling) 25mL high-pressure bottle in pass through.The flow of mobile phase is 15ml/min, and temperature is 40 DEG C, makes pressure be changed to 25MPa by 8MPa.First, 40 DEG C, dirty the stimulating the menstrual flow of condition of 8MPa be adjusted to supercritical carbon dioxide.Then be 10MPa by the pressure setting of mobile phase.Divide under the state of the pressure 10MPa of mobile phase and get component 60 minutes, then by the pressure setting of mobile phase be 15MPa and divide to get component 60 minutes, then by the pressure setting of mobile phase be 25MPa and divide to get component 60 minutes.The ratio of composition contained in each component is shown in following table 6.This component ratio utilizes ¹⁹f-N-MR determines.In addition, the composition extracted under 25MPa is few due to extraction quantity, therefore cannot analyze.

[table 6]

[embodiment 6]

In embodiment 6, use the composition comprising the compound 43 % by mole of the compound 52 % by mole of following formula (3a), the compound 5 % by mole of formula (3b) and formula (3c).

[changing 7]

F ₃C(OC ₂F ₄) _p(OCF ₂) _q-OCF ₂COOH (3a)

HOOC-CF ₂-(OC ₂F ₄) _p(OCF ₂) _q-OCF ₂COOH (3b)

F ₃C(OC ₂F ₄) _p(OCF ₂) _q-OCF ₃(3c)

Make described composition 10g using supercritical carbon dioxide as mobile phase and be filled with silica gel 60N (Northeast chemical company manufacture, pH value be 6.5 ~ 7.5 the value of 10 % by weight water slurry states (25 DEG C), particle diameter is 40 μm ~ 100 μm, dry filling) 25mL high-pressure bottle in pass through.The flow of mobile phase is 15ml/min, and temperature is 40 DEG C, makes pressure be changed to 25MPa by 8MPa.First, 40 DEG C, dirty the stimulating the menstrual flow of condition of 8MPa be adjusted to supercritical carbon dioxide.Then be 14MPa by the pressure setting of mobile phase.Divide under the state of the pressure 14MPa of mobile phase and get component 60 minutes, then by the pressure setting of mobile phase be 20MPa and divide to get component 60 minutes, then by the pressure setting of mobile phase be 25MPa and divide to get component 60 minutes.The ratio of composition contained in each component is shown in following table 7.This component ratio utilizes ¹⁹f-NMR determines.In addition, the composition extracted under 25MPa is few due to extraction quantity, therefore cannot analyze.

[table 7]

[embodiment 7]

Make the composition F 50 of 10g using supercritical carbon dioxide as mobile phase and be filled with silica gel 60N (Northeast chemical company manufacture, pH value be 6.5 ~ 7.5 the value of 10 % by weight water slurry states (25 DEG C), particle diameter is 40 μm ~ 100 μm, dry filling) 25mL high-pressure bottle in pass through.The flow of mobile phase is 15ml/min, and temperature is 40 DEG C, makes pressure be changed to 25MPa by 8MPa.First, 40 DEG C, dirty the stimulating the menstrual flow of condition of 8MPa be adjusted to supercritical carbon dioxide.Then be 12MPa by the pressure setting of mobile phase.Divide under the state of the pressure 12MPa of mobile phase and get component 60 minutes, then by the pressure setting of mobile phase be 18MPa and divide to get component 60 minutes, then by the pressure setting of mobile phase be 25MPa and divide to get component 60 minutes.The ratio of composition contained in each component is shown in following table 8.This component ratio utilizes ¹⁹f-NMR determines.

[table 8]

The feedstock composition F50 used in embodiment 7 contain 24 % by mole (relative to single end compound and two end compound total and be 31.5 % by mole) the carboxylic per-fluoro polyether compound of two ends.By in the component of said composition purifying gained, the containing ratio of the carboxylic per-fluoro polyether compound of single end is 88 % by mole.As shown in this result, if the ratio of the carboxylic per-fluoro polyether compound of two ends contained in feedstock composition is many, then the containing ratio of the carboxylic per-fluoro polyether compound of single end in component reduces.Therefore, in order to the containing ratio obtaining the carboxylic per-fluoro polyether compound of single end is the component of more than 90 % by mole, the ratio of preferably contained in the feedstock composition carboxylic per-fluoro polyether compound of two ends is less than 30 % by mole.

[embodiment 8]

Make the composition F 70 of 10g using supercritical carbon dioxide as mobile phase and be filled with silica gel 60N (Northeast chemical company manufacture, pH value be 6.5 ~ 7.5 the value of 10 % by weight water slurry states (25 DEG C), particle diameter is 40 μm ~ 100 μm, dry filling) 25mL high-pressure bottle in pass through.The flow of mobile phase is 5ml/min, and pressure is 13MPa, makes temperature be changed to 30 DEG C by 80 DEG C.First, 80 DEG C, dirty the stimulating the menstrual flow of condition of 13MPa be adjusted to supercritical carbon dioxide.Under the state of the pressure 13MPa of mobile phase, temperature 80 DEG C, point get component 60 minutes, then the temperature of mobile phase be set as 35 DEG C and point get component 60 minutes.The ratio of composition contained in each component is shown in following table 9.This component ratio utilizes ¹⁹f-NMR determines.

[table 9]

[embodiment 9]

The composition F 70 of 10g is made to be filled with silica gel 60 using supercritical carbon dioxide as mobile phase (Northeast chemical company manufactures, pH value be 5.0 ~ 7.0 the value of 10 % by weight water slurry states (25 DEG C), particle diameter is 40 μm ~ 100 μm, dry filling) 25mL high-pressure bottle in pass through.The flow of mobile phase is 15ml/min, and temperature is 40 DEG C, makes pressure be changed to 25MPa by 8MPa.First, 40 DEG C, dirty the stimulating the menstrual flow of condition of 8MPa be adjusted to supercritical carbon dioxide.Then be 12MPa by the pressure setting of mobile phase.Divide under the state of the pressure 12MPa of mobile phase and get component 60 minutes, then by the pressure setting of mobile phase be 18MPa and divide to get component 60 minutes, then by the pressure setting of mobile phase be 25MDa and divide to get component 60 minutes.The ratio of composition contained in each component is shown in following table 10.This component ratio utilizes ¹⁹f-NMR determines.In addition, the composition extracted under 25MPa is few due to extraction quantity, therefore cannot analyze.

[table 10]

As described in shown in embodiment 1 ~ embodiment 9, manufacturing method according to the invention, effectively and easily can obtain the component that the containing ratio of the carboxylic per-fluoro polyether compound of single end is high.Therefore, the containing ratio of the carboxylic per-fluoro polyether compound of single end in composition can be improved.Particularly by controlling the containing ratio of the carboxylic per-fluoro polyether compound of two ends in feedstock composition, the containing ratio of the carboxylic per-fluoro polyether compound of single end in composition can be set as more than 90 % by mole and then be set as more than 95 % by mole.

[comparative example 1]

Composition F 70 is made not use in the high-pressure bottle of the 25mL of silica gel pass through using supercritical carbon dioxide as mobile phase.The flow of mobile phase is 15ml/min, and temperature is 50 DEG C, makes pressure be changed to 20MPa by 8MPa.First, 50 DEG C, dirty the stimulating the menstrual flow of condition of 8MPa be adjusted to supercritical carbon dioxide.Then be 13MPa by the pressure setting of mobile phase.Divide under the state of the pressure 13MPa of mobile phase and get component 30 minutes, then by the pressure setting of mobile phase be 14MPa and divide to get component 30 minutes, then by the pressure setting of mobile phase be 15MPa and divide to get component 60 minutes, then by the pressure setting of mobile phase be 20MPa and divide to get component 60 minutes.The ratio of composition contained in each component is shown in following table 11.

[table 11]

As described in described in table 11, if do not use silica gel, then the content of the carboxylic per-fluoro polyether compound of single end in component cannot be set as more than 80 % by mole.Its reason is: when only carrying out supercritical extract, have the difference compared to terminal groups and utilize the difference of the molecular weight of polymer to carry out the tendency be separated.In order to improve the concentration of the carboxylic per-fluoro polyether compound of single end by means of only supercritical extract, must molecular weight distribution sharp be made, or import the large group that the dissolubility in supercritical carbon dioxide is impacted at end.In contrast, method of the present invention as described above, the component containing the carboxylic per-fluoro polyether compound of single end with high concentration can be obtained efficiently.

[comparative example 2]

Composition F 70 is made to be filled with in the high-pressure bottle of the 25mL of anion exchange resin B-20HG (manufacture of the good Nao of fine jade difficult to understand (Organo) company) to pass through using supercritical carbon dioxide as mobile phase.The flow of mobile phase is 15ml/min, and temperature is 40 DEG C, and pressure is 8MPa ~ 25MPa.Make the pressure of mobile phase be changed to 12MPa, 18MPa, 25MPa successively similarly to Example 1 by 8MPa, but the carboxylic per-fluoro polyether compound of single end cannot be extracted.

Comparative example 2 is use in Japanese Patent Laid-Open 2012-72272 publication to record the example of such anion exchange resin as Stationary liquid.As described above, because carboxylic acid is adsorbed on anion exchange resin in the method, the carboxylic per-fluoro polyether compound of single end therefore cannot be extracted.

[comparative example 3]

Make composition F 70 using supercritical carbon dioxide as mobile phase and be filled with silica gel 60N (Northeast chemical company manufacture, pH value be 6.5 ~ 7.5 the value of 10 % by weight water slurry states (25 DEG C), particle diameter is 40 μm ~ 100 μm, dry filling) 25mL high-pressure bottle in pass through.The flow of mobile phase is 15ml/min, and temperature is 40 DEG C, and pressure is 18MPa.Do not make temperature and the pressure change of mobile phase, first divide and get component 10 minutes, then divide and get component 10 minutes, divide afterwards and get component 60 minutes.The ratio of composition contained in each component is shown in following table 12.

[table 12]

As described in described in table 12, if make temperature and pressure all not change, then cannot divide and get with high concentration (namely more than 80 % by mole) containing the component at single end with the per-fluoro polyether compound of carboxyl.

[utilizability in industry]

Method of the present invention can efficiently and easily manufacture the composition containing the carboxylic per-fluoro polyether compound of single end with high concentration.In addition, manufacture method of the present invention using only manufacturing the per-fluoro polyether compound of the structure of both-terminal-functional polymer as raw material, can manufacture and contain the composition at single end with the polymer of functionality base with high concentration.In addition, method of the present invention can be applied to the polymer of the compound comprising broad molecular weight.Therefore, useful in the purifying of the raw material used at surface conditioning agent, lubricant, elastomeric material etc.

Claims

1. one kind is improved the method for the containing ratio of the carboxylic per-fluoro polyether compound of single end, it is characterized in that, the containing ratio of the carboxylic per-fluoro polyether compound of single end is improved: for the composition containing the carboxylic per-fluoro polyether compound of single end and the carboxylic per-fluoro polyether compound of two ends through following operation, carry out using the carbon dioxide of supercriticality or subcritical state as mobile phase and using silica gel as the chromatography of Stationary liquid, now, mobile phase is set as be in more than 25 DEG C and temperature between less than 150 DEG C is in more than 7MPa and the state of pressure between below 30MPa, carry out chromatography, divide and get the component containing the carboxylic per-fluoro polyether compound of single end with high concentration.

2. the method for the containing ratio of the carboxylic per-fluoro polyether compound of the single end of raising according to claim 1, is characterized in that, comprises following operation further:

I () is after point getting the operation of described component, be be in the pressure setting of mobile phase more than 7MPa and the state of pressure between below 35MPa and higher than described pressure, carry out chromatography, divide the operation of getting a large amount of components containing the carboxylic per-fluoro polyether compound of two ends; Or

(ii) after point getting the operation of described component, the temperature of mobile phase is set as being in more than 25 DEG C and is less than between 100 DEG C and the state of temperature lower than described temperature, carry out chromatography, divide the operation of getting a large amount of components containing the carboxylic per-fluoro polyether compound of two ends.

3. one kind is improved the method for the containing ratio of the carboxylic per-fluoro polyether compound of single end, it is characterized in that, for containing the carboxylic per-fluoro polyether compound of single end, the carboxylic per-fluoro polyether compound of two ends and all not there is at arbitrary end the composition of per-fluoro polyether compound of carboxyl, carry out using the carbon dioxide of supercriticality or subcritical state as mobile phase and using silica gel as the chromatography of Stationary liquid, now, through arbitrary operation of following (i ') or (ii '), improve the containing ratio of the carboxylic per-fluoro polyether compound of single end,

Mobile phase is set as being in more than 25 DEG C and temperature between less than 150 DEG C and be in more than 7MPa and be less than the state of the pressure between 30MPa by (i '), carry out chromatography, divide and get the component containing the per-fluoro polyether compound all at arbitrary end without carboxyl with high concentration, then be in the pressure setting of mobile phase more than 7MPa and the state of pressure between below 30MPa and higher than described pressure, carry out chromatography, divide the operation of getting the component containing the carboxylic per-fluoro polyether compound of single end with high concentration;

Mobile phase is set as being in more than 25 DEG C and temperature between less than 150 DEG C and be in more than 7MPa and the state of pressure between below 30MPa by (ii '), carry out chromatography, divide and get the component containing the per-fluoro polyether compound all at arbitrary end without carboxyl with high concentration, then the temperature of mobile phase be set as being in more than 25 DEG C and be less than between 150 DEG C and the state of temperature lower than described temperature, carry out chromatography, divide the operation of getting the component containing the carboxylic per-fluoro polyether compound of single end with high concentration.

4. the method for the containing ratio of the carboxylic per-fluoro polyether compound of the single end of raising according to claim 3, is characterized in that, comprises following operation further:

(i ") is after described operation (i '); be in the pressure setting of mobile phase more than 7MPa and the state of pressure between below 35MPa and higher than described pressure; carry out chromatography, point to get the operation of a large amount of components containing the carboxylic per-fluoro polyether compound of two ends; Or

(ii ") is after described operation (ii '); the temperature of mobile phase be set as being in more than 25 DEG C and be less than between 100 DEG C and the state of temperature lower than described temperature; carrying out chromatography, point to get the operation of a large amount of components containing the carboxylic per-fluoro polyether compound of two ends.

5. the method for the containing ratio of the carboxylic per-fluoro polyether compound of the single end of raising according to any one of claim 1 to 4, is characterized in that, described silica gel has the pH value of 5 ~ 7.5 with the state of 10 % by weight suspension be dispersed in water at 25 DEG C.

6. the content manufacturing the carboxylic per-fluoro polyether compound of single end is the method for the composition of more than 80 % by mole, it is characterized in that, the content manufacturing the carboxylic per-fluoro polyether compound of single end by the method for the containing ratio of the carboxylic per-fluoro polyether compound of the single end of raising according to any one of claim 1 to 5 is the composition of more than 80 % by mole.

7. the content of the carboxylic per-fluoro polyether compound of the single end of manufacture according to claim 6 is the method for the composition of more than 80 % by mole, it is characterized in that, the composition carried out before chromatography is through the operation of a part for the described carboxyl of the carboxylic per-fluoro polyether compound of two ends being fluoridized and prepares.

8. the content of the carboxylic per-fluoro polyether compound of the single end of manufacture according to claim 6 is the method for the composition of more than 80 % by mole, it is characterized in that, the composition carried out before chromatography is through following operation and prepares:

1) by operation that the part of the described functional group at two ends with the per-fluoro polyether compound of the functional group of not carboxyl is fluoridized; And

2) described operation 1 is made) functional group remaining afterwards becomes the operation of carboxyl.

9. the content of the carboxylic per-fluoro polyether compound of the single end of manufacture according to claim 8 is the method for the composition of more than 80 % by mole, it is characterized in that, functional group is acyl fluorides base.

10. the content of the carboxylic per-fluoro polyether compound of manufacture list end according to any one of claim 6 to 9 is the method for the composition of more than 80 % by mole, and it is characterized in that, per-fluoro polyether compound has following structure,

-(CF ₂) _d-(OCF ₂) _p(OCF ₂CF ₂) _q(OCF ₂CF ₂CF ₂) _r(OCF ₂CF ₂CF ₂CF ₂) _s-O(CF ₂) _d-

In formula, d is the integer of 0 or 1 ~ 5, and p, q are separately the integer of 5 ~ 300, and r, s are separately the integer of 0 ~ 100, and p+q+r+s=10 ~ 500, each unit shown in parantheses also can random bond.